Polymers and methods of making the same

ABSTRACT

An aspect of the present disclosure is a composition that includes 
     
       
         
         
             
             
         
       
     
     where R 1  includes at least one of a saturated hydrocarbon and/or an unsaturated hydrocarbon, R 3  includes at least one of a saturated hydrocarbon and/or an unsaturated hydrocarbon, A includes at least one of a saturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤1000, and 1≤y≤1000.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S Provisional PatentApplication No. 62/588,574 filed Nov. 20, 2017, the contents of whichare incorporated herein by reference in their entirety.

CONTRACTUAL ORIGIN

The United States Government has rights in this disclosure underContract No. DE-AC36-08G028308 between the United States Department ofEnergy and the Alliance for Sustainable Energy, LLC, the Manager andOperator of the National Renewable Energy Laboratory.

BACKGROUND

Plastics made of organic polymers having very high molecular weights areubiquitous in all aspects of today's society, finding applications inalmost every technology, industry, and market. One characteristic ofmost plastics is their durability. However, this durability also meansthat most plastics degrade very slowly, resulting in long lifetimes andthe eventual accumulation of plastics in landfills and, unfortunately,also in the environment. Estimates of the total human production ofplastics since the 1950s range from one billion tons to over eightbillion tons, with only about 9% of that amount recycled. Polyesters areone category of polymers defined by the presence of an ester functionalgroup in the polymer chain, with the most commonly known beingpolyethylene terephthalate (PET), which is commonly used in fibers forclothing, containers for liquids and foods, as well as in composites forproducing resins. Approximately 6 billion pounds of PET are producedannually. Greater than 80% of this annual production ends up inlandfills. Thus, methods for reclaiming polyesters such as PET providegreat opportunities for both reducing the annual amounts of wasteentering landfills, as well as opportunities for the use of recycledpolyesters for producing both reclaimed polyesters as well is new andnovel polymers and copolymers.

SUMMARY

An aspect of the present disclosure is a composition that includes

where R¹ includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon, R³ includes at least one of a saturatedhydrocarbon and/or an unsaturated hydrocarbon, A includes at least oneof a saturated hydrocarbon and/or an unsaturated hydrocarbon, 1≤x≤1000,and 1≤y≤1000.

In some embodiments of the present disclosure, the composition mayfurther include an end-group comprising at least one of hydrogen, ahydroxyl group, a halogen, and/or an ether. In some embodiments of thepresent disclosure, R¹ may further include at least one of oxygen,nitrogen, sulfur, phosphorus, and/or a halogen. In some embodiments ofthe present disclosure, R³ further may further include at least one ofoxygen, nitrogen, sulfur, phosphorus, and/or a halogen. In someembodiments of the present disclosure, A may further include at leastone of oxygen, nitrogen, sulfur, phosphorus, and/or a halogen.

In some embodiments of the present disclosure, the composition may havea structure that includes at least one of

In some embodiments of the present disclosure, the composition mayfurther include R⁵, where the composition has a structure that includes

and R⁵ is derived from a molecule having at least one vinyl group. Insome embodiments of the present disclosure, R⁵ may be derived from atleast one of styrene, styrenic divinylbenzene, acrylic acid, and/ormethacrylic acid. In some embodiments of the present disclosure, R¹ mayinclude between 1 and 10 carbon atoms, inclusively. In some embodimentsof the present disclosure, R³ may include between 1 and 10 carbon atoms,inclusively. In some embodiments of the present disclosure, A mayinclude between 1 and 10 carbon atoms, inclusively.

In some embodiments of the present disclosure, the composition mayfurther include R², where the composition has a structure that includes

and R² includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon. In some embodiments of the present disclosure,R² may further include at least one of oxygen, nitrogen, sulfur,phosphorus, and/or a halogen. In some embodiments of the presentdisclosure, R² may include between 1 and 10 carbon atoms, inclusively.

In some embodiments of the present disclosure, the structure may includeat least one of

In some embodiments of the present disclosure, the composition mayfurther include R², where the composition has a structure that includesat least one of

and R² includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon.

In some embodiments of the present disclosure, the structure may includeat least one of

In some embodiments of the present disclosure, the composition mayfurther include R⁵, where the composition has a structure that includes

and R⁵ is derived from a molecule having at least one vinyl group. Insome embodiments of the present disclosure, and R⁵ may be derived fromat least one of styrene, styrenic divinylbenzene, acrylic acid, and/ormethacrylic acid.

In some embodiments of the present disclosure, the structure may include

In some embodiments of the present disclosure, the composition mayfurther include a fiber, where the structure and the fiber form areinforced plastic. In some embodiments of the present disclosure, thefiber may include at least one of fiberglass, carbon fiber, basaltfiber, and/or a bio-derived fiber.

An aspect of the present disclosure is a method for making a polymer,where the method includes reacting maleic anhydride with a moleculehaving a first structure that includes

where R¹ includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon, R² includes at least one of a saturatedhydrocarbon and/or an unsaturated hydrocarbon, A includes at least oneof a saturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤10000, andthe reacting produces a polymer having a second structure that includes

An aspect of the present disclosure is a method for making a polymer,where the method includes reacting

with a molecule having a first structure that includes

where R¹ includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon, R² includes at least one of a saturatedhydrocarbon and/or an unsaturated hydrocarbon, A includes at least oneof a saturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤10000, andthe reacting produces a polymer having a second structure that includes

An aspect of the present disclosure is a that includes a first reactingof a molecule having a first structure with a diol that includes A,where the first structure includes

the reacting produces a second structure that includes

R¹ includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon, A includes at least one of a saturatedhydrocarbon and/or an unsaturated hydrocarbon, 1≤n≤10000, and m is lessthan n.

In some embodiments of the present disclosure, the method may furtherinclude a second reacting of the second structure with a bio-derivedmolecule having a third structure, where the third structure includes

R³ includes at least one of a saturated hydrocarbon and/or anunsaturated hydrocarbon, the second reacting produces a fourth structurethat includes

E includes at least, one of hydrogen, a hydroxyl group, a halogen,and/or an ether, 1≤x≤10000, and 1≤y≤10000.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 illustrates a method for making polymers, copolymers, resins, andreinforced plastics, according to some embodiments of the presentdisclosure.

FIGS. 2 and 3 summarize experimental results, the storage moduli ofcopolymers formed according to some embodiments of the methods describedherein.

FIG. 4 illustrates additional storage moduli data obtained bypolymerizing at least one PET-derived deconstructed molecules withmetharylic acid (squares), acrylic acid (circles), and styrene(triangles), according to some embodiments of the present disclosure.

FIG. 5 illustrates further data regarding the incorporation ofmethacrylic acid (squares) and acrylic acid (circles)cross-linker/diluents into polymers containing either of these and atleast one PET-derived deconstructed molecule, according to someembodiments of the present disclosure.

FIG. 6 compares the storage moduli of various copolymers producedaccording to some embodiments of the present disclosure.

REFERENCE NUMBERS

100 . . . method

102 . . . polyester

104 . . . diol

110 . . . polyester deconstructing

115 . . . deconstructed molecule

120 . . . treating

122 . . . purifying agent

125 . . . purified deconstructed molecule

130 . . . reacting

132 . . . bio-sourced molecule

134 . . . cross-linker/diluent

140 . . . copolymer

150 . . . resin

155 . . . fiber

DETAILED DESCRIPTION

The present disclosure may address one or more of the problems anddeficiencies of the prior art discussed above. However, it iscontemplated that some embodiments as disclosed herein may prove usefulin addressing other problems and deficiencies in a number of technicalareas. Therefore, the embodiments described herein should notnecessarily be construed as limited to addressing any of the particularproblems or deficiencies discussed herein.

The present disclosure relates to the deconstruction of polyesters, forexample reclaimed PET, to produce deconstructed molecules such as atleast one of a monomer, oligomer, and/or polymer resulting from thestarting PET. As defined herein, a “polyester” is a molecule having atleast one ester group within a chain of the molecule. As defined herein,a “macromolecule” is a large molecule having a molecular weight between1000 and 2000000 Da. Examples of macromolecules include polymers andcrosslinked polymers. A polymer may be a “homopolymer”, which refers toa polymer chain consisting of only a single type of repeat unit ormonomer, for example ethylene. A polymer may also be a “copolymer”,which refers herein to a polymer chain consisting of more than one typeof repeat unit, for example ABS, which is a copolymer constructed ofthree repeat units, acrylonitrile, butadiene, and styrene. Crosslinkedpolymers (homopolymers and/or copolymers) are referred to herein asresins, where neighboring polymer chains are covalently linked togetherby linking molecules (e.g. styrene). As used herein, the term “oligomer”refers to a relatively short-chained molecule of between 2 to 100 repeatunits.

Structure 1 illustrates an example of a polyester, according to someembodiments of the present disclosure.

R¹ in Structure 1 may include a hydrocarbon chain or branchedhydrocarbon (e.g. hydroxy propionic acid, lactic acid, orpolyhydroxybutyrate) or an aromatic group including at least one ofbenzene, anthracene, naphthalene, furan, pyridine, pyrone, pyran, and/orsubstituted aromatic groups such as hydoxy-, methoxy-, methyl-, ethyl-,butyl-, and/or propyl-substituted aromatics. In some embodiments of thepresent disclosure, R¹ may be an aromatic that further includes at leastone of nitrogen, sulfur, oxygen, phosphorous, and/or a halogen. Specificexamples of Structure 1, according to some embodiments of the presentdisclosure include at least one of

Structure 1 may be deconstructed by its reaction with a diol to producedeconstructed molecules, according to Reaction 1.

In general, Reaction 1 will result in deconstructed molecules having thegeneral structure of Structure 2, where m is the number of repeat unitsof the starting polyester, where m is less than n.

Structure 2 may be further reacted with a bio-derived molecule toproduce a copolymer, according to Reaction 2.

Reactions 3-5 illustrate examples where the bio-derived molecule iscapped with hydroxyl groups, chlorine, and ester groups respectively.

The copolymers resulting from Reactions 3-5 have the general structureof Structure 3.

Specific examples of Structure 3 include

Structure 3 may be reacted according to Reaction 6, resulting in aresin.

In some embodiments of the present disclosure, a resin may be reactedwith a fiber to produce a reinforced plastic. Suitable fibers accordingto some embodiments of the present disclosure include fiberglass, carbonfiber, basalt fiber, hemp fibers, and/or bamboo fibers.

In some embodiments of the present disclosure, a starting polyester(reclaimed or otherwise) may have between 5 and 10000 repeat unitsand/or a molecular weight between 1000 and 2000000. In some embodimentsof the present disclosure, a deconstructed molecule may have between 5and 5000 repeat units and/or a molecular weight between 200 and 100000.In some embodiments of the present disclosure, a copolymer may havebetween 5 and 10000 repeat units and/or a molecular weight between 1000and 2000000.

Structure 1 may be modified to yield Structure 4, a generalizedpolyester, according to some embodiments of the present disclosure.

In some embodiments of the present disclosure, R¹ may be a benzene groupand R² may be a —C—C— group for the example of PET. Thus, R¹ may includean aromatic group including at least one of benzene, anthracene,naphthalene, furan, pyridine, pyrone, pyran, and/or substituted aromaticgroups such as hydoxy-, methoxy-, methyl-, ethyl-, butyl-, and/orpropyl-substituted aromatics. In some embodiments of the presentdisclosure, R¹ may be an aromatic that further includes at least one ofnitrogen, sulfur, oxygen, phosphorous, and/or a halogen. R² may includeany suitable saturated and/or unsaturated, branched or straight-chainedhydrocarbon. In some embodiments of the present disclosure R² may be ahydrocarbon group having between one carbon atom and 30 carbon atoms.Thus, in some embodiments of the present disclosure a polyester,reclaimed or otherwise, may include at least one of PET, polybutyleneterephthalate, polytrimethylene terephthalate, and/or polyethylenenaphthalate, having the following general structures:

respectively.

Reactions 7-9 show generalized deconstruction reactions of a polyester,according to some embodiments of the present disclosure.

The structure for the generalized deconstructed molecule resulting fromReactions 7-9 is shown in Structure 5. Compare this to the PETdeconstructed molecule of Structure 2 above.

The deconstructed molecule of Structure 5 is shown with hydrogen and/orhydroxyl group end-groups. In some embodiments of the present disclosureStructure 5 and/or structures similar to Structure 5 may be capped withat least one of a halogen, a hydroxyl group, an alcohol, an ester, analkoxy, a diol, a multifunctional alcohol, a saturated hydrocarbon, abranched hydrocarbon, an aromatic ring, and/or an unsaturatedhydrocarbon.

Reaction 10 illustrates a generalized polymerization reaction of apolyester deconstructed molecule with a bio-derived molecule.

Reaction 10 shows the example of a bio-derived molecule having anR³-group positioned between two end-groups including an E-group. In someembodiments of the present disclosure, an R³-group of a bio-derivedmolecule may include at least one of an aromatic ring, a substitutedaromatic ring, a heteroatom substituted hydrocarbon (e.g. ketones), asaturated hydrocarbon and/or an unsaturated hydrocarbons, where thehydrocarbon may be branched and/or a straight chain. In some embodimentsof the present disclosure, the hydrocarbon may include other elements,for example, at least one of nitrogen, sulfur, oxygen, phosphorous,and/or a halogen. In some embodiments of the present disclosure Reaction10, may correspond the copolymerizing a PET deconstructed product withmuconic acid and/or a muconic acid derivative, the R³-group is anunsaturated hydrocarbon chain having two carbon-carbon double bonds anda total of four carbon atoms in a chain or a (β-ketoadipic acidcontaining a (β-ketone and a total of four carbons.

Reactions 11-13 below, illustrate examples of the copolymerization of aPET deconstructed molecule with a bio-derived molecule to formcopolymers, where the bio-derived molecule is capped with hydroxylend-groups, halogen end-groups (chlorine), and ester groups,respectively. Note that each reaction generates water, HCl, and analcohol as coproducts, respectively.

Reaction 14 illustrates another route to a copolymer, according to someembodiments of the present disclosure:

Each of Reactions 11-13 produce a copolymer having the general structureof Structure 6.

Specific examples of Structure 6 include at least one of

Other examples include

Deconstructed polyester copolymerized with a bio-derived molecule, asillustrated in Structure 6, can also be reacted with a cross-linker toform a resin, as shown in Reaction 15. In some embodiments of thepresent disclosure, a cross-linker may also serve the purpose of adiluent and/or solvent, where the copolymer is at least partiallysoluble in the cross-linker.

An example of a resin produced by Reaction 15 is Structure 7 below.

For the example of PET, PET is a hompolymer with a single repeat unithaving the structure of Structure 8:

PET may be produced by the condensation polymerization of terephthalicacid and ethylene glycol. As shown herein, in some embodiments of thepresent disclosure, PET may be deconstructed to smaller molecules bycontacting the PET with a diol, such that the diol reacts with the estergroups by transesterification, as shown below in Reaction 16.

In Reaction 16, the E-group may be any suitable end-group, for example ahalogen, a hydroxyl group, an alcohol, an ester, a diol, amultifunctional alcohol, a saturated hydrocarbon, a branchedhydrocarbon, an aromatic ring, and/or an unsaturated hydrocarbon. TheA-group in the diol may be any suitable group, for example, an aromaticring, a substituted aromatic ring, a heteroatom substituted hydrocarbon(e.g. ketones), a saturated hydrocarbon and/or an unsaturatedhydrocarbon. In some embodiments of the present disclosure a diol mayinclude at least one of ethylene glycol, propanediol, butanediol, and/orbenzene-dimethanol. Hydrocarbons may be branched chains and/orunbranched chains. The starting PET molecule, reclaimed or otherwise,may have between 10 and 10000 repeat units (e.g. 10≤n≤1000) . Reaction16 shows that the PET may be deconstructed to shorter polymer chainsand/or oligomer chains that contain the original terephthalicacid/ethylene glycol repeat unit and that some of these repeat unitswill also contain the A-group from the diol and may also be capped withhydroxyl end-groups. Hence, the A-groups from the diol are incorporatedinto polymers, oligomers, and/or monomers resulting from thedeconstruction of PET with a diol. The products from Reaction 16,referred to herein as “deconstructed molecules”, may be generalized bythe following structure, specifically for the example of deconstructedPET,

where the number of terephthalic acid/ethylene glycol repeat units inStructure 2 is some value less than the number of repeat units containedin the original source PET, Structure 1, (e.g. 1≤x≤999).

In some embodiments of present disclosure, deconstructed molecules maybe reacted with at least one “bio-sourced molecule” to produce acopolymer. This copolymerization reaction is shown Reaction 2 for theexample of copolymerizing PET deconstructed molecules with bio-sourcedmuconic acid and/or a derivative of muconic acid.

Referring to Reaction 17, the E-group may be any suitable end-group, forexample a halogen, a hydroxyl group, an alcohol, an ester, a diol, amultifunctional alcohol, a saturated hydrocarbon, a branchedhydrocarbon, an aromatic ring, and/or an unsaturated hydrocarbon.Examples of bio-sourced molecules include dicarboxylic acids,multifunctional carboxylic acids (e.g. tricarboxylic acid), diesters,multifunction esters, ketone containing molecules, lactone containingmolecules, and/or anhydrides. Examples of dicarboxylic acids suitablefor some embodiments of the present disclosure include at least one ofcis,cis-muconic acid, cis,trans-muconic acid, trans, trans-muconic acid,succinic acid, fumaric acid, malic acid, 2,5 furan dicarboxylic acid, 3hydroxy propionic acid, aspartic acid, glucaric acid, glutamic acid,β-keto adipic acid, α-keto adipic acid, β-keto glutaric acid, α-ketoglutaric acid, and/or adipic acid. Suitable esters, anhydrides, and acylhalides include esters, anhydrides, and acyl halides of the carboxylicacids named above. For example, a suitable diester that may be used inReaction 17 is the diester of trans, trans-muconic acid or cis,cis-muconic acid, trans, trans-dimethyl muconate and cis,cis-dimethylmuconate. An example of anhydride molecules is maleic anhydride.

Whether or not a reactant or product described herein is “bioderived”may be determined by analytical methods. Using radio carbon and isotoperatio mass spectrometry analysis, the bio-based content of materials canbe determined. ASTM International, formally known as the AmericanSociety for Testing and Materials, has established a standard method forassessing the biobased content of carbon-containing materials. The ASTMmethod is designated ASTM-D6866. The application of ASTM-D6866 to derivea “biobased content” is built on the same concepts as radiocarbondating, but without use of the age equations. The analysis is performedby deriving a ratio of the amount of radiocarbon (14C) in an unknownsample to that of a modern reference standard. The ratio is reported asa percentage with the units “pMC” (percent modern carbon). If thematerial being analyzed is a mixture of present day radiocarbon andfossil carbon (containing no radiocarbon), then the pNMC value obtainedcorrelates directly to the amount of biomass material present in thesample. Thus, ASTM-D866 may be used to validate that the compositionsdescribed herein are and/or are not derived from renewable sources.

Referring again to Reaction 17, the resulting copolymer may beconstructed of deconstructed molecules covalently linked to neighboringbio-sourced molecules by the A-group of the diol. Depending on thereaction conditions of Reaction 17, the copolymer may include at leastone of the following structures: -ABABABAB-, -AABBAABB-, -[A]n[B]m- , ora random copolymer where the A subunits and B subunits are randomlydistributed through the chains of the copolymer, or amultiblock-copolymer where large regions are composed of the samesubunit. So, for the example of Reaction 17, subunit A corresponding toStructure 1, and subunit B, having the

structure originating from muconic acid and/or a muconic acidderivative, may alternate in any form of an alternating block copolymerand/or each of the subunits may be randomly distributed along thecopolymer chains. Such copolymers may be represented by the generalstructure shown in Structure 10. The same copolymer structure applies tothe other copolymer embodiments described herein.

Further, in some embodiments of the present disclosure, a copolymerresulting from the depolymerization of a polyester, for example,Structure 10 for PET copolymerized with muconic acid and/or a muconicacid derivative, may be reacted with a cross-linker (e.g. styrene),either during the copolymerization reaction (for example Reaction 17)and/or in a separate subsequent reaction, resulting in the formation ofa resin, as shown above in Reaction 15 for the example of deconstructingPET and copolymerizing the PET deconstructed molecules with muconic acidand/or a muconic acid derivative, resulting in Structure 7. Examples ofcross-linkers include styrene, styrenic divinylbenzene, acrylic acid,methacrylic acid, substituted styrenes, styrenic derivatives, methylmethacrylate, methyl acrylate, esters of acrylic acid, esters ofmethacrylic acid, and/or any suitable vinyl functionalized molecule. Insome embodiments of the present disclosure, for example Structure 7above, R⁵ may be a benzene ring, a carboxylic acid, an ester, anaromatic ester, a hydrocarbon, and/or any other suitable structure. Insome embodiments of the present disclosure R⁵ may include more than onevinyl group, a sulfur group, and/or any other suitable crosslinkingstructure. In some embodiments of the present disclosure, a cross-linkermay also serve the purpose of a diluent and/or solvent, where thecopolymer is at least partially soluble in the cross-linker.

In some embodiments of the present disclosure, a polyester may bedeconstructed with a diol to produce at least one deconstructedmolecule, where the polyester may be deconstructed in the melt (e.g.where the polymer is the primary component), neat (e.g. in a solutioncomprised solely of the deconstruction agent) and/or in solution using asolvent (e.g. typically a none reactive solvent such as DMSO). Thereaction can occur between 30 minutes and 12 hours, with or without acatalyst (e.g. a catalyst may include an esterification ortransesterification catalyst such as titanium (IV) butoxide or StannousOctoate), with stirring/mechanical agitation, at a temperature betweenroom temperature up to 400C, under nitrogen purge or vacuum, and/or insolvents under reflux.

In some embodiments of the present disclosure, deconstructed moleculemay be reacted with a bio-derived molecule to form a copolymer, wherethe polymerization is performed neat and/or in solution using a solvent.The reaction can take place under mechanical agitation at a temperaturebetween 100 C and 400 C, either under nitrogen purge or vacuum, for aperiod from 1 minute to 12 hours, and with or without catalyst (e.g. acatalyst may include an esterification or transesterification catalystsuch as titanium (IV) butoxide or Stannous Octoate). In some embodimentsof the present disclosure, a copolymer may be cross-linked using across-linker to produce a resin, where the reacting to form the resin isperformed neat and/or in solution using a solvent, with an initiator(e.g. free-radical, ionic, etc.) or under UV, at a temperature betweenambient and 200 C, for a period between 1 minute and 2 days.

In some embodiments of the present disclosure, maleic anhydride may bering-opened according to Reaction 18 below, and subsequently reactedwith a polyester deconstructed molecule to produce a copolymer accordingto Reaction 19.

In some embodiments of the present disclosure, a polyester deconstructedmolecule may be reacted according to Reaction 20.

In some embodiments of the present disclosure, PET, reclaimed orotherwise, may be deconstructed (depolymerized) using at least onereactant, for example a diol. The resultant deconstruction products,referred to herein as deconstructed molecules, may include at least oneof a PET-derived monomer, oligomer, and/or polymer, for example,mono-hydroxy ethyl terephthalate (MHET), bis-2-hydroxyethylterephthalate (BHET), oligomers and/or polymers thereof. For example, adeconstructed molecule resulting from the deconstruction of PET may bean oligomer and/or polymer of MHET ethyl benzene-1,4-dicarboxylate.

In some embodiments of the present disclosure, a PET-deriveddeconstructed molecule resulting from the deconstruction reaction of PETwith a reactant (e.g. diol) may be transformed into a macromolecule,wherein the term “macromolecule”, as used herein, refers to any polymer(e.g. homopolymer, copolymer, etc.), cross-linked polymer (e.g. resin),reinforced polymer and/or resin (e.g. fiberglass reinforced plastic(FRP), and/or combinations thereof. For example, in some embodiments ofthe present disclosure, macromolecules having structures similar tounsaturated polyesters (UPE) and/or vinyl esters (VE), may be producedby reacting a PET-derived deconstructed molecule with at least onebioderived monomer. Examples of bioderived monomers include bioderivedcarboxyl group-containing molecules such as at least one of muconicacid, fumaric acid, methacrylic acid, and/or acrylic acid. Otherexamples of bioderived monomers include the esters of bioderivedcarboxyl group-containing molecules (e.g. where the carboxyl group isconverted to an ester group.) In addition, a bioderived monomer may besaturated and/or unsaturated (e.g. containing at least one carbon-carbondouble bond and/or carbon-carbon triple bond). In some embodiments ofthe present disclosure, a first macromolecule in the form of at leastone of a polymer and/or a copolymer (e.g. a UPE and/or a VE) may besimultaneously and/or subsequently reacted with a cross-linker (e.g.styrene, methacrylic acid, and/or acrylic acid) around a reinforcingmatrix (e.g. woven mat, such as a fiberglass) to produce a secondmacromolecule, a reinforced plastic, for example, a fiberglassreinforced plastic (FRP). As shown herein, for the examples ofmethacrylic and acrylic acid as cross-linkers, the resultant FRPs havedemonstrated favorable processability and final properties. In someembodiments of the present disclosure, a first macromolecule in the formof at least one at least one of a polymer and/or a copolymer may besimultaneously and/or subsequently reacted with a cross-linker to form asecond macromolecule, for example, a resin.

In some embodiments of the present disclosure, at least onedeconstructed molecule resulting from the deconstruction of PET, forexample terephthalic acid, ethylene glycol, BHET, and/or MHET, and/or aPET polymer (e.g. virgin PET, deconstructed PET, and/or reclaimed PET)may be reacted with at least one bioderived monomer and/or homopolymerthat contains rigid moieties (e.g. poly(butylene (β-keto adipate,keto-glutaric acids, and/or any other suitable) to produce biodegradablemacromolecules that may provide environmentally friendly PETalternatives. As shown herein, a comparison of polyethylene topoly(butylene adipate-co-terephthalate) (PBAT), a biodegradablealternative to polyethylene, the presence of rigid and biodegradablemoities provide the PBAT polymers with physical and performanceproperties comparable to PET (e.g. glass transition, meltingtemperature, permeability, etc.). The demonstrates the feasibility of ofreplacing, at least partially, PET macromolecules with comparablebiodegradable polymers.

In some embodiments of the present disclosure, PET may be deconstructedto a terephthalate ester (e.g. dimethyl terephthalate), which may thenbe converted to a dinitrile and subsequently to a diamine. The diaminemay then be directly blended with reclaimed PET, or with neatterephthalic acid, terephthaloyl chloride, and/or a terephthalate ester,to synthesize a polyaramid which may possess properties similar tocommercially available polyaramids (e.g. Kevlar).

In some embodiments of the present disclosure, reclaimed PET may beconverted to a diester and/or diacid, which may be subsequentlyconverted to a diol. This diol may then undergo a wide variety oftransformations such as dehydration to form divinyl benzene and/ordirect reaction with a difunctional monomer (e.g. carbamate) to form apolymer (e.g.polycarbonate).

FIG. 1 illustrates a method 100 for producing materials (eithercopolymers and/or fiberglass reinforced plastics/FRPs) 140 based on thereacting 130 of a bio-sourced monomer/oligomer/polymer 132 with apolyester-derived monomer/oligomer/polymer; a deconstructed molecule115. The polyester-derived deconstructed molecule 115 may be obtained,for example, by depolymerizing reclaimed PET, as described herein. Insome embodiments of the present disclosure, a reclaimed polyester 102may be deconstructed (e.g. depolymerized) by reacting the reclaimedpolyester 102 with a diol 104. In some embodiments of the presentdisclosure a diol, may be supplemented and/or replaced with a base, asalt, an alcohol, and/or a diamine.

In some embodiments of the present disclosure, the polyesterdeconstructing 110 may be achieved by loading a solid polyester with adiol 104 (e.g. ethylene glycol, hexanediol, and/or butanediol) and asuitable catalyst (e.g. at least one of titanium butoxide, sodiummethoxide, a Lewis basic catalyst, and/or a transesterificationcatalyst) and heating the resultant mixture to an elevated temperature(e.g. up to or near the boiling point of the diol; e.g. 220° C.) undermechanical stirring and inert conditions. The resultant mixturecontaining at least one polyester-derived deconstructed molecule 115 maybe directed to a treating 120 step to purify the deconstructed molecule115 by removing any unreacted diol 104 (e.g. and/or other materials)and/or any impurities (e.g. colorants), resulting in the formation of atleast one purified PET-derived deconstructed molecule 125. In someembodiments of the present disclosure, the treating 120 may includedirecting a treating component, for example, a purifying agent 122, tothe treating 120 step, to be mixed with the at least of thedeconstructed molecules 115. The treating component, e.g. purifyingagent, 122 may be any suitable liquid, gas, and/or solid. In someembodiments of the present disclosure, the purifying agent 122 may be aliquid, including at least one of water and/or an organic liquid. Thetreating 120 may be achieved by any suitable unit operation, includingliquid extraction, filtration, distillation, etc.

Referring again to FIG. 1, according to some of the embodimentsdescribed above, at least one purified polyester-deconstructed molecule125, e.g. at least one of a MHET monomer, oligomer, and/or polymerand/or at least one of a BHET monomer, oligomer, and/or polymer thereof,may be mixed with at least one bio-sourced molecule 132, for example, adicarboxylic olefinic acid and/or and anhydride to produce a copolymer140, for example, an unsaturated polyester. In some embodiments, and/orin addition to, at least one purified polyester-derived deconstructedmolecule 125 may be reacted with at least one bio-sourced molecule 132,for example, a monocarboxylic olefinic acid to produce a copolymer 140,for example, a vinyl ester. Referring again to FIG. 1, across-linker/diluent 134 may be directed to the reacting 130, whereinthe cross-linker/diluent 134 may react with at least one of the purifiedpolyester-derived deconstructed molecules 125 and/or the at least onebio-sourced molecules 132, such that the cross- linker/diluent 134 isincorporated into the resultant copolymer 140. In addition to reactingwith at least one of the purified polyester-derived deconstructedmolecules 125 and/or at least one of the bio-sourced molecules 132, thecross-linker/diluent 134 may act as a solvent in which the polymerizingreactions may occur. It should be noted that in some embodiments of thepresent disclosure, the method 100 shown in FIG. 1, may not include thetreating 120 step.

FIGS. 2 and 3 summarize experimental results, the storage moduli ofcopolymers formed according to some embodiments of the methods describedherein. Specifically, reclaimed PET was deconstructed to form at leastone PET-derived monomer/oligomer/polymer, which was subsequentlycombined and polymerized with several bio-sourced monomers and across-linker/diluent. For these experiments, the bio-sourced monomersincluded muconic acid, maleic anhydride, and fumaric acid. In addition,polymerization with at least one PET-derived monomer/oligomer/polymerwas also tested with styrene as the cross-linker/solvent. FIGS. 2 and 3illustrate that muconic acid, maleic anhydride, and fumaric acid wereeach successfully incorporated into copolymers containing at least onePET-derived monomer/oligomer/polymer, and several examples ofbiodegradable UPE PET alternatives were successfully synthesized. FIG. 4illustrates additional storage moduli data obtained by polymerizing atleast one PET-derived monomer/oligomer/polymer with metharylic acid(squares), acrylic acid (circles), and styrene (triangles). FIG. 5provides further data regarding the incorporation of methacrylic acid(squares) and acrylic acid (circles) cross-linker/diluents into polymerscontaining either of these and at least one PET-derivedmonomer/oligomer/polymer. In the case for the UPE the experimentalresults demonstrate no dependence on deconstruction/molecular weight.However, for the vinyl ester version, in which a monocarboxylic acid isused, the properties depend on molecular weight.

FIG. 6 compares the storage moduli of various copolymers producedaccording to some embodiments of the present disclosure. The left threecolumns were made using styrene as the cross-linker/diluent, whereas theright four columns were made using methacrylic acid as thecross-linker/diluent. PET refers to copolymers produced by polymerizingethyl benzene-1,4-dicarboxylate with various bio-sourcedmonomers/oligomers/polymers, whereas rPET refers to copolymers producedusing monomers/oligomers/polymers derived from reclaimed PET with thesame bio-sourced monomers/oligomers/polymers. The comparisons shown inFIG. 6 illustrate that the rPET copolymers demonstrate essentiallyidentical storage moduli as the PET copolymers. FIG. 6 also illustratesthat copolymers having higher storage moduli resulted from the use ofmethacrylic acid as the cross-linker/diluent, whereas styrene as thecross-linker/diluent performed less favorably, where both themethacrylic acid and the styrene act as both a solvent and across-linker; e.g. as reactive diluents.

Scheme 1 illustrates another embodiment of the present disclosure, abiodegradable PET alternative, where v and w may be any integer valuebetween 1 and 1000.

In this example, the adipic acid of PBAT may be replaced with a monomerand/or polymer that is more rigid than adipic acid, in this examplebutylene-β-keto adipate, to produce a modified copolymer, indicated hereas PBKAT. Table 1 below summarizes the glass transition temperatures andmelting temperatures of PET and PBKAT at different molar loadings ofbutylene-β-keto adipate.

TABLE 1 Polymer T_(g) T_(m) PET 70 260 PBKAT - 5% 70 260 PBKAT - 10% 70260 PBKAT - 20% 70 260 PBKAT - 50% 70 260 PBKAT 70 —

Thus, the present disclosure relates to a variety of unique copolymersderived from the polymerization of at least one PET-derivedmonomer/oligomer/polymer derived from at least one of neat monomers,virgin PET, and/or reclaimed PET (e.g. at least one of MHET and/or BHETmonomers and/or oligomers and/or polymers thereof) with at least onebio-sourced monomer/oligomer/polymer, e.g. with at least one of adicarboxylic acid, a monocarboxylic acid, and/or an anhydrides, withspecific examples including at least one of muconic acid, fumaric acid,β-keto adipic acid, and/or maleic anhydride.

EXAMPLES

PET Deconstruction: PET was deconstructed with butanediol or ethyleneglycol. Initially, PET was placed into a round bottom flask affixed witha condenser. Variable amounts of the diol were loaded into the reactorwith 0.5 wt % titanium butoxide and the reactor was heated up to 220° C.The transesterification reaction proceeded under reflux for 4 hours.Following the reaction, the slurry was removed from the reactor andwashed with an excess of water to remove unreacted diol and any ethyleneglycol that was removed via transesterification. The polymer-watermixture was subsequently filtered, and the solid polymer precipitate wasvacuum dried for 24 hours to remove excess moisture and diol.

Homopolymer Synthesis: Initially, poly(ethyleneterephthalate-co-fumarate), poly(ethylene terephthalate-co-malate), andpoly(ethylene terephthalate-co-muconate) were synthesized via melttransesterification with reclaimed PET bottles. Initially, the reactor(a three-necked round bottom flask attached with nitrogen, overheadmechanical stirring motor, and Dean-Stark condenser setup) was loadedwith a fixed molar ratio of deconstructed PET todiacid/diester/anhydride and 0.5 wt % titanium butoxide as thetransesterification catalyst. The reaction vessel was heated to 180° C.and polymerization was allowed to proceed for 6 hours. This preventedmolecular weight growth of the polymer chain while allowing the olefinicmonomers to be incorporated into the polymer backbone.

To synthesize the virgin-PET copolymers, the reactor was loaded with 1.1molar equivalents of diol to 1 molar equivalent of totaldiacid/diester/anhydride with no transesterification catalyst. Thereaction vessel was initially heated to 180° C. and polymerization wasallowed to proceed for 1 hour. After an hour, the temperature wasincreased to 220° C., vacuum was applied to the system, and the reactionwas allowed to proceed for 5 hours. This resulted in a polymer with amolecular weight on the order of 3*10⁴ g/mol that was used in comparisonto the deconstructed PET.

Diacrylic Polymer Synthesis: The reactor was initially loaded with 40 wt% PET and 60 wt % olefinic acid (acrylic or methacrylic acid) and wasallowed to reflux for 6 hours. Following reflux, AIBN (the free radicalinitiator) was added to the reaction mixture which was subsequentlyaliquoted for direct use in composite synthesis.

Fiberglass Reinforced Plastic (FRP) Synthesis: Composites were preparedby either preparing a solution of 39.5 wt % olefinic polymer and 59.5 wt% olefinic acid with 1.0 wt % AIBN as an initiator, or by mixing thefinal vinyl ester solution. The reaction mixture was applied to 2-plyBondo™ fiberglass mat, placed between two sheets, and allowed to reactfor 6 hours at 80° C. Following the reaction, the fiberglass was placedin a vacuum oven for at least 48 hours to allow for any excess monomerto evaporate. Samples were weighed after vacuum drying and nosignificant weight loss was observed.

Structural Characterization: Polymer structure was ascertained via aBruker Avance III HD 400 MHz NMR Spectrometer with a 5 mm BBO probe.Quantitative ¹H spectra were acquired with a 90° pulse of 14.5 μs and a30 s recycle delay at room temperature. Deuterated trifluoroacetic acid(99.9% Cambridge Isotope Lab) with 1% w/w TMS was used as the solvent.Molecular weight was determined via the use of a Wyatt GPC equipped witha Tosoh Column, Multiangle Light Scatter, and RI detector. HFIP was usedas the elution solvent at a flow rate of 0.5 mL/min.

Physical Property Testing: After vacuum drying, the composites were cutinto a 60×12×2 mm pieces for mechanical testing. Mechanical tests wereperformed on a TA Instruments Q800 Dynamic Mechanical Analyzer at 35° C.across a range of frequencies from 0.01 to 10 Hz. Thermalcharacterization was completed by the use of a TA Instruments Q1000Digital Scanning calorimeter and a Q500 Thermogravimetric Analyzer usingramp rates of 10° C/min.

The foregoing discussion and examples have been presented for purposesof illustration and description. The foregoing is not intended to limitthe aspects, embodiments, or configurations to the form or formsdisclosed herein. In the foregoing Detailed Description for example,various features of the aspects, embodiments, or configurations aregrouped together in one or more embodiments, configurations, or aspectsfor the purpose of streamlining the disclosure. The features of theaspects, embodiments, or configurations, may be combined in alternateaspects, embodiments, or configurations other than those discussedabove. This method of disclosure is not to be interpreted as reflectingan intention that the aspects, embodiments, or configurations requiremore features than are expressly recited in each claim. Rather, as thefollowing claims reflect, inventive aspects lie in less than allfeatures of a single foregoing disclosed embodiment, configuration, oraspect. While certain aspects of conventional technology have beendiscussed to facilitate disclosure of some embodiments of the presentinvention, the Applicants in no way disclaim these technical aspects,and it is contemplated that the claimed invention may encompass one ormore of the conventional technical aspects discussed herein. Thus, thefollowing claims are hereby incorporated into this Detailed Description,with each claim standing on its own as a separate aspect, embodiment, orconfiguration.

1. A composition comprising:

wherein: R¹ comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon, R³ comprises at least one of a saturatedhydrocarbon or an unsaturated hydrocarbon, A comprises at least one of asaturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤1000, and1≤y≤1000.
 2. The composition of claim 1, further comprising an end-groupcomprising at least one of hydrogen, a hydroxyl group, a halogen, or anether.
 3. The composition of claim 1, wherein R¹ further comprises atleast one of oxygen, nitrogen, sulfur, phosphorus, or a halogen.
 4. Thecomposition of claim 1, wherein R³ further comprises at least one ofoxygen, nitrogen, sulfur, phosphorus, or a halogen.
 5. The compositionof claim 1, wherein A further comprises at least one of oxygen,nitrogen, sulfur, phosphorus, or a halogen.
 6. The composition of claim1 having a structure comprising at least one of


7. The composition of claim 1, further comprising R⁵, wherein: thecomposition has a structure comprising

and R⁵ is derived from a molecule having at least one vinyl group. 8.The composition of claim 7, wherein R⁵ is derived from at least one ofstyrene, styrenic divinylbenzene, acrylic acid, or methacrylic acid. 9.The composition of claim 1, wherein R¹ comprises between 1 and 10 carbonatoms, inclusively.
 10. The composition of claim 1, wherein R³ comprisesbetween 1 and 10 carbon atoms, inclusively.
 11. The composition of claim1, wherein A comprises between 1 and 10 carbon atoms, inclusively. 12.The composition of claim 1, further comprising R², wherein: thecomposition has a structure comprising

and R² comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon.
 13. The composition of claim 12, wherein R²further comprises at least one of oxygen, nitrogen, sulfur, phosphorus,or a halogen.
 14. The composition of claim 12, wherein R² comprisesbetween 1 and 10 carbon atoms, inclusively.
 15. The composition of claim12, wherein the structure comprises at least one of


16. The composition of claim 1, further comprising R², wherein: thecomposition has a structure comprising at least one of

and R² comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon.
 17. The composition of claim 16, wherein thestructure comprises at least one of


18. The composition of claim 12, further comprising R⁵, wherein: thecomposition has a structure comprising

R⁵ is derived from a molecule having at least one vinyl group.
 19. Thecomposition of claim 18, wherein R⁵ is derived from at least one ofstyrene, styrenic divinylbenzene, acrylic acid, or methacrylic acid. 20.The composition of claim 18, wherein the structure comprises


21. The composition of claim 18, further comprising a fiber, wherein thestructure and the fiber form a reinforced plastic.
 22. The compositionof claim 21, wherein the fiber comprises at least one of fiberglass,carbon fiber, basalt fiber, or a bio-derived fiber.
 23. A method formaking a polymer, the method comprising: reacting maleic anhydride witha molecule having a first structure comprising

wherein: R¹ comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon, R² comprises at least one of a saturatedhydrocarbon or an unsaturated hydrocarbon, A comprises at least one of asaturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤10000, and thereacting produces a polymer having a second structure comprising


24. A method for making a polymer, the method comprising: reacting

with a molecule having a first structure comprising

wherein: R¹ comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon, R² comprises at least one of a saturatedhydrocarbon or an unsaturated hydrocarbon, A comprises at least one of asaturated hydrocarbon or an unsaturated hydrocarbon, 1≤x≤10000, and thereacting produces a polymer having a second structure comprising


25. A method comprising: a first reacting of a molecule having a firststructure with a diol comprising A, wherein: the first structurecomprises

the reacting produces a second structure comprising

R¹ comprises at least one of a saturated hydrocarbon or an unsaturatedhydrocarbon, A comprises at least one of a saturated hydrocarbon or anunsaturated hydrocarbon, 1≤n≤10000, and m is less than n.
 26. The methodof claim 25, further comprising: a second reacting of the secondstructure with a bio-derived molecule having a third structure, wherein:the third structure comprises

R³ comprises at least one of a saturated hydrocarbon or an unsaturatedhydrocarbon, the second reacting produces a fourth structure comprising

E comprises at least one of hydrogen, a hydroxyl group, a halogen, or anether, 1≤x≤10000, and 1≤y≤10000.